Chemical composition

ABSTRACT

IT IS DISCLOSED THAT GEL FORMATION IN LIQUID DETERGENTS CONTAINING OLEFIN SULFONATES OF 12 TO 16 CARBON ATOMS PER MOLECULE CAN BE AVOIDED BY THE PRESENCE OF ALKALI METAL, AMMONIUM OR ETHANOL AMMONIUM SALTS OF HYDROXYALKANE SULFONIC ACIDS HAVING FROM 2 TO 7 CARBON ATOMS PER MOLECULE IN SAID SYSTEMS. TYPICAL SYSTEMS MAY INCLUDE IN ADDITION TO THE OLEFIN SULFONATE AND THE HYDROXYALKANE SULFONIC ACID SALT, OTHER DETERGENT ACTIVES SUCH AS ALKYL ETHER SULFATES, TERTIARY AMINE OXIDES, AMIDES, ETHANOL AMIDES AND OTHER CONVENTIONAL DETERGENT ACTIVES AND ADJUVANTS.

United States Patent 3,808,156 CHEMICAL COMPOSITION Richard D. Gorsich,Melvin E. Tuvell, and William J.

Dewitt, Baton Rouge, La., assignors to Ethyl Corporation, Richmond, Va.No Drawing. Filed Nov. 22, 1971, Ser. No. 201,197 Int. Cl. Clld 1/14,1/83, N84 US. Cl. 252-545 12 Claims ABSTRACT OF THE DISCLOSURE It isdisclosed that gel formation in liquid detergents containing olefinsulfonates of 12 to 16 carbon atoms per molecule can be avoided by thepresence of alkali metal, ammonium or ethanol ammonium salts ofhydroxyalkane sulfonic acids having from 2 to 7 carbon atoms permolecule in said systems. Typical systems may include in addition to theolefin sulfonate and the hydroxyalkane sulfonic acid salt, otherdetergent actives such as alkyl ether sulfates, tertiary amine oxides,amides, ethanol amides and other conventional detergent actives andadjuvants.

BACKGROUND OF THE INVENTION Field of the invention This inventionrelates to liquid detergent compositions containing olefin sulfonates inaqueous systems and is directed to the avoidance of the gel formationproblem characteristic of aqueous systems containing ole-fin sulfonates.In accordance with the teachings of the present invention, the gelformation problem is avoided or materially reduced by using in suchaqueous olefin sulfonate systems a soluble salt of a hydroxy-alkanesulfonic acid and in particular one wherein the hydroxy group is anomega hydroxy group and wherein the alkane structure contains form 2 toabout 6 carbon atoms.

Description of the prior art Although light duty liquid detergentformulations containing LAS (linear alkyl aryl sulfonate) have been usedon a large scale for many years, particularly for dishwashing, it hasbeen discovered that it is not possible to directly substitute olefinsulfonates for the LAS in such prior formulations or in similar onesbecause the resulting compositions have a tendency toward the formationof gels in storage in containers or in dispensers used for suchformulations. The simple inexpensive dispensers familiar to most of thepeople who use liquid dishwashing detergents contain a metering orrestriction arrangement such as an orifice or small diameter passage orport which retains at least a residual quantity of liquid detergent incontact with the air after each usage aggravates the gelling problem.Thus olefin sulfonates have been characterized by unlikely acceptancebecause of difficulty of use in the conventional manner familiar to thehousewife. Despite the attractiveness of an olefin sulfonate baseddetergent from biodegradability and cost-effectiveness viewpoints, suchcannot be used if it cannot be removed from the container in an easy andconventional manner.

The bottle-cap dispenser is an example of a widelyused type of dispenserthat is prone to pluggage due to the formation of gels with olefinsulfonates. To hold costs low, this dispenser usually contains a simplearrangement of a flow passage having a diameter of from severalmillimeters up to about 10 or 20 millimeters, typically millimeters. Thesmall diameter and exposed position relative to air provides aparticularly adverse combination of conditions prone to gellation.

Olefin sulfonate detergents are generally used as formulationscontaining other detergent materials. A typical 3,808,156 Patented Apr.30, 1974 containing higher R alkyl groups such as lauryl and myristyl (CH and (C I-I groups. Although the olefin sulfonates may be used informulations containing only one of the aforementioned AES, amine oxideor amide materials, a particularly preferred formulation is aformulation which contains both ABS and amides or both ABS and amineoxide together with the olefin sulfonates.

Other conventional detergent active and adjuvant materials normallypresent in light duty formulations such as the foregoing includecoupling agents which typically are lower alkanols such as ethanol;dyes; perfumes; water softeners; etc. Such systems are generally madeinto aqueous systems containing 50-75 wt. percent water providing aliquid detergent which is not prohibitively expensive to transport andis easy and convenient to use except for the problem of gelling whichmanifests itself usually as pluggage of the small diameter cap meteringpassage after only several uses; however, some systems such as the amineoxide containing systems are so prone to gelling that they form gels onstorage even in the bottle itself.

SUMMARY OF THE INVENTION Once the gelling problem was discovered,attempts were made to solve it using numerous approaches; however, allefforts met with little or no success until it was discovered that thegellation problem could be avoided with the conventional prior artdescribed ADS-containing systems by the addition of a comparativelysmall amount of a hydroxy alkane sulfonate compound of the formula Inthis formula, n is 1 to 6, preferably 1 or 2 particularly 1; and M is analkali metal, ammonium or ethanol ammonium cation. Once this discoverywas made, numerous formulations involving wide ranges of proportions ofthe ingredients discussed were tested including formulations havingvarious percentages and ratios of ABS, amine oxide and amide todetermine the proportions of components which can be dispensed throughconventional metering cap systems without undue gelling tendencies.

The amount of anti-gelling compound useful for the anti-gellingcapability ranges from about 1 to about 15 percent by weight of theliquid detergent formulation. A preferred range is from about 3 to about10 percent by weight, about 5 percent by weight being particularlypreferred. On a ratio basis, the ratio of detergent actives relative tothe HOCH (CH ),,SO M is from about 2:1 to about 30:1.

In accordance with the present invention, a particularly preferredanti-gelling additive is sodium isethionate or beta hydroxyethanesulfonic acid sodium salt and which has the formula HOCH CH SO Na. Othertypical additives include omega hydroxypropane sulfonic acid potassiumsalt, omega hydroxyisopropane sulfonic acid sodium salt, omegahydroxybutane sulfonic acid sodium salt, omega hydroxypentane sulfonicacid potassium salt, omega hydroxyhexane sulfonic acid monoethanolammonium salt, omega hydroxybutane sulfonic acid ammonium salt, betahydroxyethane sulfonic acid triethanol ammonium salt, omegahydroxypropane sulfonic acid diethanol ammonium salt.

The hydroxyalkane can be produced by any suitable pror art process. Forexample, the production of beta hydroxyethane sulfonic acid sodium saltis described by Lauer and Hill in Journal of the American ChemicalSociety, vol. 58, p. 1873 (1936). This compound is produced by reactingNaHSO with ethylene oxide.

The olefin sulfonate used is typically an alkali metal, ammonium orethanol ammonium salt of a mixture of alkene and hydroxyalkanesulfonates having from about 12 to about 16 carbon atoms per molecule.It is obtained by reacting olefin with gaseous uncomplexed S in a ratioof about 1 mol of S0 per mol of olefin followed by a saponification withan appropriate base such as NaOH, preferably at temperatures of fromabout 100 to about 150 C. As disclosed in U.S. Pat. 3,332,876, olefinsulfonates are produced typically by a reaction of the olefin in aliquid S0 diluent system or in a gaseous diluent system. An example ofthe former is U.S. Pat. 2,061,617 while examples of the latter are U.S.Pats. 2,697,031 and 3,169,- 142.

Preferred sulfonates are those which are predominantly of a structurewith a sulfonate group attached to a terminal C atom. Sulfonates whosesulfonate group are attached to non-terminal carbon atoms such as thoseproduced by the sulfonation of internal olefins are also desirable,particularly when such are components of mixed systems containingderivatives of vinyl, vinylidene and internal types of olefins. Suchsulfonates are characterized as being of substantially open chain carbonskeleton structures.

Although the derivatives of pure olefins may be used or may be producedseparately and blended into mixtures as herein described, thesulfonation of mixtures of olefins is preferred, typically mixtureshaving up to about 20 percent C 2, up to about 100 percent C and up toabout 80 percent C and which contain predominantly straight chainterminal olefins plus from about 3 to about 30 mol percent of betabranched terminal olefins and from about 3 to about 12 mol percent ofinternal olefins, the latter preferably being predominantly straightchain. Such preferred olefins are typically obtained by the so-calledZiegler process of chain-growth with ethylene on a lower trialkylaluminum compound to produce a higher alkyl trialkyl aluminum asdescribed in U.S. Pat. 2,826,598, followed by an ethylene displacementliberating the desired higher molecular weight olefins. Such an ethylenedisplacement is described in U.S. Pat. 3,389,161. The process is alsodescribed in Annalen der Chemie, vol. 629, Nos. 1-3, pp. 172-198. Theolefins thus obtained are acyclic in structure and almost exclusivelymono olefins.

The sulfonates thus produced are essentially acyclic and contain a widespectrum of open chain compounds in two general classes of unsaturatedand hydroxyalkane compounds some of which have two or more sulfonic acidgroups and which frequently are called disulfonates. The compounds arepredominantly alkene sulfonates and hydroxyalkane sulfonates many ofwhich are described individually or in groups in U.S. Pats. 2,061,617;2,061,- 618; 2,061,619; 2,061,620; 2,160,343; 2,187,244; 2,365,- 783;2,383,737; 2,383,738; 2,486,922; 2,529,538; 2,923,- 728; 3,169,142;3,259,645; 3,270,038; 3,328,460; 3,332,- 880; 3,346,505; 3,350,428;3,384,597; 3,409,637; 3,420,- 875; 3,424,693; 3,424,694; 3,428,654;3,444,087; 3,444,- 191; 3,488,384; 3,506,580; 3,531,518; 3,535,339;3,544,- 475; 3,565,809; and Re. 22,548.

The alcohol ether sulfate component optionally used in compositions inaccordance with the present invention is typically obtained as anaqueous system of the product of sulfntion of ethoxylated alcohols withchlorosulfonic acid.

4 The alcohols ethoxylated are pure alkanols or mixtures of As mentionedalso in U.S. Pat. 3,332,876, the alkyl ether prior literature, such areless preferred in connection with U.S. Pats. 3,384,651 and 3,415,861.The ethoxylated derivatives preferably average from about 1 to about 5ethylene oxide units per molecule.

As mentioned also in U.S. Pat. 3,332,876, the alkl ether sulfates can bemade by the condensation by known methods of ethylene oxides on tomonohydric alcohols from various natural or synthetic sources and having10 to 18 carbon atoms per molecule. Molar proportions of ethylene oxideto alcohol are generally 1 to 5. The resulting ethoxylated alcohol isthen sulfated and neutralized with an appropriate base such as alkalimetal hydroxide, ammonium hydroxide of ethanol ammonium base. Althoughthe alkaline earth metal salts are generally discussed in priorliterature such are less preferred in connection with the presentinvention.

The amide component used in formulation in accordance with the presentinvention are fatty acid amides and fatty acid monoand di-lower alkanolamides having from about 10 to about 14 carbon atoms in the fatty acidalkyl groups, particularly those having also lower alkanol groups offrom 2 to 6 carbon atoms such as lauryl monoethanol amide, myristyldiethanol amide, myristyl mono isopropanol amide and lauryldiisopropanol amide. In such amides, the alkyl groups present arepreferably pure individual or mixed coconut range alkyls, typically amixed alkyl distribution of a whole cut coconut oil or of a center cutcoconut oil.

Suitable amides and their methods of production are well known to thoseskilled in the art as shown, for example, by U.S. Pats. 2,607,740 and3,332,878, both of which, like all other patents and literature citedherein are herewith incorporated by reference.

Amine oxides suitable for use in the compositions of the presentinvention are conventional detergent components Whose structures andmethods of preparation are well known to those skilled in the art asdisclosed for example by US. Pats. 2,169,976; 3,001,945; 3,234,282;3,317,430; 3,397,239 and by Canadian Pat. 847,303.

Typical and preferred amine oxides are long chain dimethyl amine oxidessuch as lauryl dimethyl amine oxide and myristyl dimethyl amine oxide.

To provide a standard of comparison, prior art LAS formulations arediscussed in Soap and Chemical Specialties, September 1967, p. 108.Therein are disclosed the following compositions.

Percent LAS 10 25 AES 5 10 Na xylene sulfonate 4 10 Laurie monoethanolamide- 2 5 Ethanol 3 12 Water. Balance Balance Total- 100 DISCUSSION OFTHE INVENTION CLAIMED in R and R are lower alkyl radicals or hydroxyalkyl radicals having from 1 to about 4 carbon atoms and R is asaturated aliphatic radical having from about to about 20 carbon atoms,(3) an alkyl ether sulfate having the formula RO(C H O),,SO M, wherein Ris an alkyl chain of from about 10 to about 18 carbon atoms; x is avalue from 1 to about 5, the cation of said sulfonate and the cation ofM of such sulfate being independently selected from the group consistingof alkali metal, ammonium and ethanol ammonium; plus (C) a hydroxyalkanesulfonate of the formula HOCH (CI-I ),,SO M', wherein n is from 1 toabout 6 and the cation M is alkali metal, ammonium or ethanol ammoniumand (D) water. The composition contains from about to about 60 percentby weight of A+B+C, the proportions of A to B being from about 15:1 toabout 1:1 on a weight basis and the weight ratio of A+B to C being fromabout 2:1 to about 30:1.

In a preferred aspect of the present invention, the hydroxyalkanesulfonate is beta hydroxyethane sulfonic acid, sodium salt.

In preferred embodiments of the present invention a coupling agent isused which preferably is a lower alkanol having up to about 6 carbonatoms per molecule. A preferred alkanol is ethyl alcohol. Other suitablealkanols include normal propyl alcohol, isopropyl alcohol, butylalcohols, amyl alcohols, and hexyl alcohols. The coupling agent is usedin proportions of up to about 15 percent by weight based on thecomposition, more preferably from about 2 to about 10 percent by weight,on the same basis.

In a preferred aspect of the present invention, the mono olefinsulfonate is the product of the saponification with NaOH of the productof sulfonation of predominantly straight chain terminal olefins withuncomplexed S0,; in proportions of from about 0.9 to about 1.1 mols ofS0 per mol of olefin.

In a preferred aspect of the present invention, the predominantlystraight chain terminal olefins used in the sulfonation contain fromabout 3 to about 30 percent on a mol basis of beta-branched terminalolefins and from about 3 to about 12 percent on a mol basis of internalolefins. Preferably the internal olefins are substantially all straightchain.

In a preferred aspect of the present invention, the proportionsofComponents A, B and C on a weight basis are from about 15 to about 30percent, from about 10 to about percent, and from about 1 percent toabout 10 percent, respectively.

In accordance with a preferred aspect of the present invention, theproportions of Components A, B and C on a weight basis are from about 15to about 30 percent, from about 10 to about 20 percent, and from about 1percent to about 15 percent, respectively, and the Component B is amixture of alkyl ether sulfate as defined in the foregoing and fattyacid monoor di-lower alkanol amide as described in the foregoing in aweight ratio of from about 4:1 to about 2:1 of alkyl ether sulfaterelative to amide.

In accordance with a preferred aspect of the present invention, theproportions of A, B and C on a weight basis are from about 15 to about30 percent, from about 10 to about 20 percent, and from about 1 percentto about 10 percent, respectively, and the Component B is a mixture ofalkyl ether sulfate and tertiary amine oxide in weight ratio of fromabout 4: l to about 2:1 of alkyl ether sulfate relative to tertiaryamine oxide.

In a particularly preferred combination in accordance with the presentinvention, Component A is the product of saponification with NaOH of theproduct of sulfonation with uncomplexed S0,, of a mixture ofpredominantly straight chain terminal olefins having from about 12 toabout 16 carbon atoms per molecule. In this preferred embodiment,Component B is a mixture of alkyl ether sulfate and lauryl dimethylamineoxide or, alternately,

myristyl dimethyl amine oxide in a weight ratio of about 3:1, andComponent C is beta hydroxyethane sulfonic acid, sodium salt. In thispreferred embodiment, the proportions of Components A, B and C on aweight basis are about 21 percent, about 16 percent, and about 5percent, respectively, and the system contains about 5 percent ethylalcohol as coupling agent. Particularly preferred compositions inaccordance with this embodiment contain the usual proportions of otherconventional detergent adjuvants and actives including perfume, dye,water softeners, etc. as described in the patents cited herein.

Formulations of olefin sulfonates in accordance with the presentinvention preferably are made into aqueous systems ranging from about 50to about 75 percent water on a weight percent basis providing a more orless thick liquid system.

The detergent active ingredients mentioned as well as the hydroxyalkanesulfonic acid Component (C) are for the most part used in the form ofsolids added to water to ultimately result in a system of the desiredwater content. An exception to this is the alcohol ether sulfate whichis usually obtained in an aqueous solution of about 60 wt. percent AESconcentration. On an anhydrous adjuvantfree weight percent basis,preferred compositions of the present invention are expressed broadly as40-70' percent olefin sulfonate, 5-40 percent alcohol ether sulfate and1-20 percent amide.

The lower alkanol described as useful as a coupling agent, typicallyethanol, may be replaced wholly or partially by humectants such aspropylene glycol, glycerine and sorbitol.

EXAMPLES The following detergent formulations were made and tested bydispensing from a 12 oz. plastic bottle having a screw-on cap containinga tubular passage therein of approximately 5 millimeters diameter and 20millimeters length. grams of each formulation was used for the tests.Three times each day at about 8:00 a.m., 12:00 noon and 4:00 pm. thebottle was inverted and squeezed so as to discharge about 2 cc. of thedetergent sample contained therein. Following each discharge, the bottlewas replaced in an upright position and allowed to stand, the capportion being uppermost. This procedure was continued until thedischarge passage became blocked with gel or until the contents of thebottle were exhausted. All samples shown as containing betahydroxyethane sulfonic acid, sodium salt, successfully passed the bottlecap test for gelling. All samples that did not have beta hydroxyethanesulfonic acid, sodium salt failed by pluggage of the discharge passagewithin two or three days after the start of the test.

The AES was Alfonic l4-12A ether sulfate manufactured by Continental OilCompany. It is based on 3 mols ethoxylate of a mixture of mainlydodecanol and tetradecanol in a 40/60 ratio by weight, as the ammoniumsalt.

The lauryl dimethyl amine oxide was Aromox (Armour Industrial ChemicalCo.) DMMCDW containing 1.0 percent C 70.0 percent C 24 percent C 5percent C by weight distribution of the long chain alkyl groups.

The monoethanol amide was Stepan Ninol AA-62 Extra.

The beta hydroxyethane sulfonic acid, sodium salt was GAF SodiumIsethionate manufactured by General Aniline and Film Company.

The A08 was a C /C olefin derivative.

The A08 used was the product of saponification at C. with NaOH of theproduct of sulfonation with gaseous S0 in a falling-film reactor at 30C. of olefins (Wt. percent C 0.4; C -66.2; C 33.4; average C No. 14.6,average MW 205) (mol percent by NMR vinyl79.2; vinylidene12.5;internal-8.2) produced by displacement of the product of chain growth ofethylene or triethyl aluminum.

EXAMPLE I [Weight percent of components shown] A B C D E F G H I J AES12. 7 s 12 o 12. 7 s. o 0 12. 0 o Ethanol- 6.0 e o. 0 e s. 9 6.0 s. o6.0 a. 0 s. 9

LMMEA- 0 0 6.3 0 0 0 0 6.3 0 0 Amine oxide 0 0 0 4 5. 0 0 0 0 4. 0 5. 0

Beta hydroxy ethane sulfonlc acid, sodium salt.... 8. 0 6 6. 0 6 5. 9 00 0 0 0 A09 25. 3 18 31. 7 21 28. 1 25. 3 18. 0 31. 7 2l. 0 28. 1 Watm-Balance Balance Balance Balance Balance Balance Balance Balance BalanceBalance Total 100. 0 100 100. 0 100 100. 0 100. o 100. 0 100. 0 100. 0100. 0

EXAMPLE II (C) a hydroxyalkane sulfonate of the formula: A quickscreening test was provided for determining 2 z)n s the gellingcharacteristics of detergent formulations. The wherein n is from 1 toabout 6, and the cation M components of the formulations were asdescribed in Example I. A glass plate approximately 70 cm. in length wasplaced with one end thereof 17.5 centimeters higher than the otherforming an inclined plane surface. A portion of the detergentformulation to be tested was placed upon the glass plate near the upperend and the flow characteristics that resulted were evaluated. In thoseinstances where a smooth substantially straight downward flow along theplate was obtained, the material under test was rated as having asatisfactory performance with regard to anti-gelling, the resultscorrelating closely with the bottle cap test. An unsatisfactoryperformance with regard to anti-gelling was indicated by the presence ofa very irregular flow pattern as a gel film formed on the forward edgeof the downward flowing stream causing the material to fiow sideways toby-pass the obstructions resulting from the gel formation. Again inevery instance tabulated herein the compositions using betahydroxyethane sulfonic acid, sodium salt were found to produce testresults indicative of suitable non-gelling properties for the sodiumisethionate-containing compositions in contrast to unsatisfactorygelling properties for the similar compositions that did not containbeta hydroxyethane sulfonic acid, sodium salt.

is alkali metal, ammonium or ethanol ammonium, and

(D) water, said composition containing from about 15 to about 60 percentby weight of A+B+C, the proportions of A to B being from about 15:1 toabout 1:1 on a wt. basis and the weight ratio of A plus B to C beingfrom about 2:1 to about 30:1.

2. The composition of claim 1 wherein the hydroxy alkyl sulfonate isbeta hydroxyethane sulfonic acid, sodium salt.

3. The composition in accordance with claim 1 containing a couplingagent in proportions of up to about 15 percent by weight of thecomposition.

4. The composition of claim 3 wherein the coupling agent is ethylalcohol.

5. The composition of claim 1 wherein the monoolefin sulfonate is theproduct of the saponification with NaOH of the product of sulfonation ofpredominantly straight chain terminal olefins with uncomplexed 80;, inproportions of from about 0.9 to about 1.1 mols of S0 per mol of olefin.

6. The composition of claim 1 wherein the predominantly straight chainterminal olefins used in the sulfona- EXAMPLE H [Weight percent ofcomponents shown] A B C D E F G H I .1

[UPS 16 3 10 9 6 16 3 10 9 6 Ethanol 12 6 15 10 15 12 6 15 10 15 T.MM1 A0 0 4 0 0 0 0 4 0 0 LMDF A 6 9 0 2 4 6 9 0 2 4 Beta hydroxy ethanesulionic acid, sodium salt-... 4 6 8 6 7 0 0 0 0 0 AOS 1e 20 25 25 2c 1620 25 25 2e Wam- Balance Balance Balance Balance Balance Balance BalanceBalance Balance Balance Total 100 100 100 100 100 100 100 100 100 100What is claimed is: 1. A gel resistant liquid detergent compositionconsisting essentially of:

(A) a monoolefin sulfonate having from about 12 to about 16 carbon atomsin the molecule; (B) at least one of:

(1) fatty acid monoor di-lower alkanol amide, the fatty acid groupscontaining from about 10 to about 14 carbon atoms, (2) tertiary amineoxide of the formula tion contain from about 3 to about 30 percent on amol basis of beta branched terminal olefins and from about 3 to about 12percent on a mol basis of internal olefins.

7. A composition in accordance with claim 1 wherein the proportions ofComponents A, B and C on a weight basis are from about 15 to about 30percent, from about 10 to about 20 percent, and from about 1 percent toabout 10 percent, respectively.

8. A composition in accordance with claim 1 wherein the proportions ofComponents A, B and C on a weight basis are from about 15 to about 30percent, from about 10 to about 20 percent, and from about 1 percent toabout 15 percent, respectively and wherein the Component B is a mixtureof 3 and 1 in weight ratio of from about 4:1 to about 2:1.

9. A composition in accordance with claim 1 wherein the proportions ofComponents A, B and C on a weight basis are from about 15 to about 30percent, from about 10 to about 20 percent, and from about 1 percent toabout 10 percent, respectively and wherein the Component B is a mixtureof 3 and 2 in weight ratio of from about 4: 1 to about 2:1.

10. A composition in accordance with claim 1 wherein Component A is theproduct of saponification with NaOH of the product of sulfonation withuncomp exed of a mixture of predominantly straight chain terminalolefins having from about 12 to about 16 carbon atoms per molecule,wherein Component B is a mixture of alkyl ether sulfate andlauryldimethyl amine oxide in a wt. ratio of about 3:1, whereinComponent C is beta hydroxyethane sulfonic acid, sodium salt, whereinthe proportions of Components A, B and C on a weight basis are about 21percent, about 16 percent, and about 5 percent, respectively and whereinthe system contains about 5 percent ethyl alcohol as coupling agent.

11. The composition in accordance with claim 1 containing a loweralaknol having up to about 6 carbon atoms per molecule in proportions ofup to about 15 percent by weight of the composition.

12. The composition of claim 11 wherein the lower alkanol is ethylalcohol.

References Cited UNITED STATES PATENTS LEON D. ROSDOL,

Sweeney 252-55 5 Primary Examiner P. E. WILLIS, Assistant Examiner US.Cl. X.R.

ran STATES PATENT OFFICE QEREEFECATE CE CCRECTEON Inventor(s)' RichardD. Gors ich, Melvin E. Tuvell and William J. Dewitt 7 It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

T "I Column 2, line 7, reads amines oxide", should read amine oxide;line 9, reads "amides should read amides Column 5, line 7 reads pror",should read prior- Column i, lines 1-6, should read The alcoholsethoxylated are pure alkanols or mixtures of alcohols ranging from about10 to about 18 carbon atoms per molecule. Typical mixtures of alcoholsare center cut or whole cut coconut alcohols of natural or syntheticorigin, preferably synthetic as produced in accordance with U. S.Patents 5,584,651 and 3,415,861. The ethoxylated derivatives preferablyaverage from about 1 to about 5 ethylene oxide units per molecule -5line 7, reads "alkl", should read alkyl Column 9, line 12, reads"alaknol", should read alkanol Signed and sealed this 12th day ofNovember 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner ofPatents

